Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
  • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
  • C08G65/3255—Ammonia
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
  • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic

Definitions

• the present invention relates in general to the reductive amination of hydroxy-containing compounds, and in particular to the reductive amination of polyether polyols to produce high molecular weight amines.
• 6586 which discloses a process for the production of an amine by reacting at elevated temperature a first reactant which is either an alcohol, an aldehyde or a ketone with a second reactant which is either ammonia, a primary or a secondary amine or a nitrile in the presence as catalyst of a composition comprising (i) nickel, (ii) ruthenium, and (iii) at least one other transition metal selected from either the second or third row transition metals.
• Alcohols which are useful in the aforesaid process are alkanols containing no more than 30 carbon atoms, alkoxypolyethylene glycols containing no more than 30 carbon atoms and diols or polyols and their ether and polyether derivatives, provided that the total number of carbon atoms does not exceed 30 in the case of a primary alcohol.
• Amines, and particularly the higher molecular weight amines are useful in the manufacture of polyurethanes by reaction with isocyanates and epoxy coatings by reaction with epoxides.
• the direct formation of the higher molecular weight amines by reductive amination has hitherto been impossible to achieve in the case of the high molecular weight polyether alcohols having one, two or more hydroxy functions at least one of which is a primary hydroxyl group or only achievable under forcing reaction conditions, for example pressures greater than 750 psig, for other higher molecular weight alcohols.
• Representative of the art relating to the high pressure process may be mentioned in U.S. Pat. Nos. 3,838,076, 4,181,682, 3,847,992, 4,612,335 and 4,618,717.
• U.S. Pat. No. 4,181,682 claims a polymer composition comprising a polymeric amine having the following structural formula: ##STR1## where x is an average number ranging from about 6 to 50, and y and z are average numbers ranging from about 1 to about 20 with the sum of y and z being from 6 to about 40.
• the disclosure at column 2, lines 38 to 47, reads as follows:
• the present invention provides a process for the production of an amine by reacting in the presence of hydrogen at elevated temperature a first reactant which is a compound substantially involatile at the elevated temperature employed and having either one, two or more hydroxyl functions, each of which is independently either a primary or secondary hydroxyl function, with a second reactant which is either ammonia or a primary or a secondary amine in the presence of a reductive amination catalyst wherein the reaction is effected in either a continuously or periodically open system.
• a first reactant which is a compound substantially involatile at the elevated temperature employed and having either one, two or more hydroxyl functions, each of which is independently either a primary or secondary hydroxyl function
• a second reactant which is either ammonia or a primary or a secondary amine in the presence of a reductive amination catalyst wherein the reaction is effected in either a continuously or periodically open system.
• hydrogen and the second reactant in the gaseous phase are contacted at elevated temperature either continuously or intermittently with the first reactant in the liquid phase, optionally in the presence of a solvent, and a reductive amination catalyst to form a product comprising an amine, water and unreacted gas, and from the product there is removed either continuously or intermittently water and unreacted gas.
• the water and unreacted gas removed from the product may be separated either wholly or partially, suitably by condensing the water, and the unreacted gas so-separated may be recycled to the reaction.
• the process can be operated at atmospheric pressure which may provide advantages in terms of lower capital expenditure and operating costs, when compared with the prior art elevated pressure processes.
• Another unexpected important advantage of operating according to the invention is that improved selectivities to desirable products can be achieved.
• a selectivity loss occurs. This may be demonstrated by reference to the reaction of a polyether polyol with a primary amine as the aminating species in which the following reactions are believed to occur: ##STR2##
• Reaction (1) is the reaction desired.
• the self-condensation reactions (2) and (4) not only waste amine but also, more importantly, lead to reaction (3) which produces an unwanted by-product not readily separable from the desired secondary amine terminated polyether. In the open system according to the present invention, this selectivity loss is substantially eliminated.
• the first reactant is a compound substantially involatile at the elevated temperature employed and having either one, two or more hydroxyl functions, each of which is independently either a primary or secondary hydroxyl function.
• the compound may be a monohydric alcohol, suitably an alkanol of the formula: ##STR3## wherein R 1 is hydrogen, and
• R 2 and R 3 are either aliphatic alkyl groups or substituted aliphatic alkyl groups.
• the compound may be a dihydric alcohol, suitably a diol, for example ethylene glycol, propylene glycol, butylene glycol, alkylene glycols, polyalkylene glycols, mixed polyalkylene glycols and their ether and polyether derivatives.
• a dihydric alcohol suitably a diol, for example ethylene glycol, propylene glycol, butylene glycol, alkylene glycols, polyalkylene glycols, mixed polyalkylene glycols and their ether and polyether derivatives.
• the compound may be a polyhydric alcohol, suitably a polyhydric alcohol having more than two hydroxyl groups, each being attached to a substituted carbon atom.
• Suitable examples of polyhydric alcohols include glycerol and triethanolamine.
• a preferred class of compound is the polyether alcohols, including polyether monools, polyether diols and polyether polyols. Generally, these are high molecular weight materials, typical molecular weights being in the range from about 200 to 10,000. It is an advantage of the invention that polyether amines can be derived from polyether alcohols having primary hydroxyl functions.
• the second reactant there may be used either ammonia or a primary or secondary amine.
• the amine may be either an aliphatic or an aromatic amine.
• the amine may be a primary aliphatic amine.
• the amine may suitably contain from 1 to 30 carbon atoms.
• Hydrogen of commercial purity may be used, with or without further purification.
• Nickel-containing catalysts are preferred. Powdered elemental nickel, Raney nickel and supported nickel, for example nickel supported on gamma-alumina, may all be used as catalysts.
• a preferred catalyst is a composition comprising (i) nickel, (ii) ruthenium, and (iii) at least one other transition metal selected from either the second or third row transition metals.
• any transition metal other than ruthenium may be used as component (iii).
• ⁇ transition metal ⁇ is defined as a metal having a partially filled 4d or 5d shell in at least one of its oxidation states. Suitable transition metals include palladium, rhenium and iridium, either individually or in combination.
• the catalyst composition is supported on a suitable support.
• suitable supports include aluminas, silicas, silica-aluminas and carbons.
• a preferred support is gamma-alumina. Zeolites may also be used as supports.
• the major component will generally be component (i), i.e. nickel, and components (ii), i.e. ruthenium, and (iii) i.e. transition metal(s) will be minor components.
• nickel may suitably form from 50 to 95% by weight of the catalyst composition and together ruthenium and transition metal may form the remainder of the composition.
• the supported catalyst composition may contain about 10% nickel and 1% each of ruthenium and transition metal(s), the remainder of the composition being the support. However, higher nickel loadings may be used if desired.
• the catalyst composition may be prepared by any of the methods conventionally employed for the production of catalysts, for example by precipitation or by impregnation.
• the supported composition is suitably prepared by an impregnation technique, which may be by co-impregnation or by sequential impregnation, preferably the latter.
• Impregnation techniques are well-known in the art and include both the incipient wetness technique and the excess solution technique.
• a preferred process for producing a catalyst composition for use in the process of the present invention comprises the steps of (A) impregnating a support with a solution of a compound of nickel, (B) calcining the nickel compound present in the impregnated support obtained in step (A), (C) impregnating the impregnated support obtained in step (B) with a solution of a compound of a transition metal selected from either the second or third row transition metals, (D) impregnating the impregnated support obtained in step (C) with a solution of a compound of ruthenium, and (E) activating the composition obtained in step (D).
• the catalyst may be contacted with either hydrogen or air at elevated temperature.
• the elevated temperature may suitably be in the range from 250° to 500° C., preferably from 250° to 350° C., for contact with hydrogen and from 500° to 600° C. for contact with air.
• Suitable compounds of the metals include salts of the metals, for example the nitrates, halides and carboxylates.
• the compounds of the metals are used in the form of solutions thereof. Any suitable solvent may be employed for this purpose.
• a convenient solvent is water, though other solvents, such as for example alcohols, may be employed.
• step (B) of the process for producing the catalyst the compound of nickel present in the impregnated support obtained in step (A) is calcined. Calcination may suitably be accomplished at a temperature in the range from 550° to 600° C., typically about 580° C., though lower temperatures may be employed.
• Activation may suitably be accomplished by heating the composition at elevated temperature, suitably greater than 280° C. in the presence of a reducing gas, for example hydrogen, for a period sufficient to activate the catalyst, typically for at least 3 hours and thereafter allowing the catalyst to cool in the presence of an inert gas, for example nitrogen.
• the activation step (step E) may be carried out as a further step in the preparative method, or may be carried out in the reductive amination reactor immediately prior to operation of the process of the invention, or both.
• the process may be operated at a temperature in the range from 150° to 350° C., preferably from 180° to 300° C. Atmospheric pressure or slightly above may suitably be employed.
• the process may be operated batchwise or continuously. Generally, it will be necessary to separate the catalyst from the liquid product of the reaction. This may suitably be accomplished by filtration or centrifugation.
• Example 1 The reaction described in Example 1 was performed using 20 g of polyether polyol type C1634, having molecular weight around 4800 and 3 primary hydroxyl functions. Analysis by 13 C NMR showed over 50% amination of the polyol. Reaction with a diisocyanate gave very rapid crosslinking typical of a polyether polyamine.
• test was performed in a sealed system under reaction conditions more typical of the prior art.
• the Test demonstrates the lower selectivity to desired product obtained in a closed system.

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• Chemical & Material Sciences (AREA)
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• Polymers & Plastics (AREA)
• Inorganic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Citations (25)

• 1988
  • 1988-08-18 GB GB888819663A patent/GB8819663D0/en active Pending
• 1989
  • 1989-08-03 EP EP19890307925 patent/EP0356046A3/de not_active Withdrawn
  • 1989-08-04 US US07/389,748 patent/US5015773A/en not_active Expired - Fee Related
  • 1989-08-10 AU AU39498/89A patent/AU3949889A/en not_active Abandoned
  • 1989-08-11 PT PT91444A patent/PT91444A/pt not_active Application Discontinuation
  • 1989-08-15 JP JP1209727A patent/JPH02117646A/ja active Pending

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